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VOLUME 1
NUMBER 2
TM
Molecular Self-Assembly
Introduction to
Molecular Self-Assembly
Self-Assembled
Monolayers (SAMs)
Microdisplacement
Printing
Self-Assembly in
Flexible Electronics
Biotechnology
Biosensor Program
sigma-aldrich.com
Introduction
Welcome to the second issue of Material MattersTM. This thematic issue focuses on self- TM
assembly and its application for the production of nanodevices. The ability to organize
matter using self-assembled monolayers (SAMs) is part of the broader approach of
Molecular Self-Assembly as introduced by Dr. Jasty of Sigma-Aldrich Materials Science. Vol. 1 No. 2
Scientists from Assemblon discuss the importance of purity in enhancing the integrity
and kinetics of SAMs formation. The Weiss group from Penn State University illustrates
the principle of microdisplacement printing, a SAMs technique to fabricate precise, Aldrich Chemical Co., Inc.
complex patterns at the nanoscale. Prof. Bao of Stanford University surveys the Sigma-Aldrich Corporation
latest developments in the application of SAMs for the fabrication of organic thin 6000 N. Teutonia Ave.
film transistors. Borrowing a basic concept of biomolecular recognition, polyvalent Milwaukee, WI 53209, USA
interactions, the team at Sensopath Technologies engineers robust NanotethersTM as the
SAMs molecules for biosensor and other applications. We invite you to participate in
the Sigma-Aldrich Biosensor program. Finally, in keeping with the theme of a technical To Place Orders
Introduction
guide, this issue of Material Matters includes a step-by-step protocol for the preparation Telephone 800-325-3010 (USA)
of SAMs. Products that accelerate your research in the fundamental science of SAMs, FAX 800-325-5052 (USA)
and the application of SAMs for the fabrication of nanodevices are highlighted. For
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What would it take to spontaneously assemble a computer chip, or for that matter any
complex structure? Starting with constituent molecules such as the one featured on
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our cover, (11-Mercaptoundecyl)tri(ethylene glycol), and with recent advances in micro-
and nanoscale science, scientists from numerous disciplines, chemistry, physics, biology,
Material Matters is a publication of Aldrich Chemical
engineering, and mathematics to name a few, have begun to investigate the self-assembly
Co., Inc. Aldrich is a member of the Sigma-Aldrich
process in hopes of learning to create, design and control self-assembling systems.
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Self-Assembly
Introduction to Molecular
the shape and properties of the molecules that are used, as of virtually any desired chemistry by placing a gold substrate
compared to traditional techniques, such as lithography, where into a millimolar solution of an alkanethiol in ethanol. This
the desired final structure must be carved out from a larger results in crystalline-like monolayers formed on the metal
block of matter. Self-assembly is thus referred to as a ‘bottom- surface, called self-assembled monolayers (SAMs).1
up’ manufacturing technique, as compared to lithography Over the years, the mechanism of the self-assembly process
being a ‘top-down’ technique. has been well studied and elucidated. Researchers have found
On a molecular scale, the accurate and controlled application that a typical alkanethiol monolayer forms a (√3 × √3)R30°
of intermolecular forces can lead to new and previously structure2 on gold with the thiol chains tilted approximately 30
unachievable nanostructures. This is why molecular self- degrees from the surface normal.3–6 The exact structure of the
assembly (MSA) is a highly topical and promising field of monolayer depends on the chemistry of the chain.
research in nanotechnology today. With many complex Self-assembly forms the basis for many natural processes
examples all around us in nature (ourselves included), MSA including protein folding, DNA transcribing and hybridization,
is a widely observed phenomenon that has yet to be fully and the formation of cell membranes. The process of self-
understood. Biomolecular assemblies are sophisticated and assembly in nature is governed by inter- and intra-molecular
often hard to isolate, making systematic and progressive forces that drive the molecules into a stable, low energy
analyses of their fundamental science very difficult. What in state. These forces include hydrogen bonding, electrostatic
fact are needed are simpler MSAs, the constituent molecules of interactions, hydrophobic interactions, and van der Waals forces.
which can be readily synthesized by chemists. These molecules
As with self-assembly in nature, there are several driving forces
would self-assemble into simpler constructs that can be easily
for the assembly of alkanethiols onto noble metal surfaces. The
assessed with current experimental techniques.
first is the affinity of sulfur for the gold surface. Researchers
O r d e r :
Of the diverse approaches possible for Molecular Self-Assembly, have found that the sulfur-gold interaction is on the order of 45
two strategies have received significant research attention kcal/mol,3 forming a stable, semi-covalent bond; in comparison,
– Electrostatic Self-Assembly (or layer- by-layer assembly) the C—C bond strength is ~83 kcal/mol.
and “Self-Assembled Monolayers (SAMs). Electrostatic self-
1 . 8 0 0 . 3 2 5 . 3 0 1 0
The next driving force for assembly is the hydrophobic, van
assembly involves the alternate adsorption of anionic and
der Waals interactions between the methylene carbons on
cationic electrolytes onto a suitable substrate. Typically, only
the alkane chains. For alkanethiol monolayers, this interaction
one of these is the active layer while the other enables the
causes the thiol chains to tilt in order to maximize the
composite multilayered film to be bound by electrostatic
interaction between the chains and lower the overall surface
attraction. The latter strategy of Self Assembled Monolayers
energy. A well-ordered monolayer forms from an alkane chain
or SAMs based on constituent molecules, such as thiols and
of at least 10 carbons. With carbon chains of this length,
silanes, is the theme for this second issue of Material MattersTM.
hydrophobic interactions between the chains can overcome the
For SAMs, synthetic chemistry is used only to construct the
molecules’ rotational degrees of freedom.6,7
basic building blocks (that is, the constituent molecules), and
Te c h n i c a l
weaker intermolecular bonds such as Van der Waals bonds A simple alkanethiol molecule is shown in Figure 1. (next
are involved in arranging and binding the blocks together into page) An alkanethiol can be thought of as containing 3 parts:
a structure. This weak bonding makes solution, and hence a sulfur binding group for attachment to a noble metal surface,
reversible, processing of SAMs (and in general, MSAs) possible. a spacer chain (typically made up of methylene groups, (CH2)n),
Thus, solution processing and manufacturing of SAMs offer and a functional head group. As mentioned above, the sulfur
the enviable goal of mass production with the possibility of atom and the carbons in the methylene groups act as the main
S e r v i c e :
error correction at any stage of assembly. It is well recognized driving forces for assembly of the alkanethiols. The head group
that this method could prove to be the most cost-effective then provides a platform where any desired group can be used
way for the semiconductor electronics industry to produce to produce surfaces of effectively any type of chemistry.
functional nanodevices such as nanowires, nanotransistors, and By simply changing the head group, a surface can be created
nanosensors in large numbers. that is hydrophobic (methyl head group), hydrophilic (hydroxyl
1 . 8 0 0 . 2 3 1 . 8 3 2 7
Head
undecyl)tetra(ethylene glycol) and correlated the solution
Group concentration to the surface concentration using electron
Head Group spectroscopy for chemical analysis (ESCA) and Time-of-
Flight Secondary Mass Spectrometry (ToF-SIMS).8 This study
demonstrated how the surface and solution composition in
Spacer Group mixed monolayers can vary significantly and why a calibration
curve is necessary when engineering mixed monolayer
surfaces.
Terminal
Sulfur As a demonstration of the effects of thiol impurities in SAM
formation, Table 1 shows ESCA surface composition data
Group from a series of SAMs prepared from thiol solutions that
C12 Thiol
were purposely spiked with “impurities”. For this experiment,
Substrate solutions of (1-mercapto-11-undecyl)tetra(ethylene glycol)
SH
(PEG4 thiol, Aldrich Prod. No. 674508) were mixed with 0%,
Self-Assembled
of Pure Alkanethiols
Monolayers: Advantages
Figure 1. Schematic diagram of a thiol molecule. 1% and 10% (v/v) thioacetic acid (TAA). All monolayers
The sulfur group links the molecule to the gold surface. The head group can were prepared from 1 mM solutions in absolute ethanol.
be designed to provide virtually any surface chemistry, binding capacity, or The percentages shown for the various thiol components are
property.
volume percentages.
Self-Assembly: Purity Matters The first observation noted from Table 1 is the increase in
SAMs are typically made from a 1 mM solution of the desired the atomic percentage of gold with increasing amount of
alkanethiol in ethanol. Initial monolayer formation is very fast, thioacetic acid in the assembly solution. The gold signal comes
with monolayer coverage being achieved within seconds to from the gold substrate underlying the monolayer. This gold
minutes. This initially formed monolayer is not well ordered signal is attenuated by the overlying monolayer film. A thinner
and contains many gauche defects within the chains. Over or more disordered overlayer causes a decrease in signal
time, the layers become more ordered and well packed. attenuation (increase in the gold signal). This suggests that the
Reported assembly times vary throughout the literature, but addition of even 1% thioacetic acid to the assembly solution
typically are 12 hours to 2 days. caused a marked decrease in the monolayer thickness.
Thioacetic acid is a small molecule which if inserted into the
The formation of a well-assembled monolayer can depend on monolayer would disrupt the local monolayer order causing
the purity of the alkanethiol being used. The presence of even the noted decrease in the layer thickness.
low levels of contaminants can result in a disordered, non-
ideal monolayer. Many typical impurities in thiol compounds Table 1. ESCA composition data from PEG4 thiol monolayers with and
without “impurities”. All data is shown in atomic percent. Two analysis
are thiolated precursor molecules that were not separated spots are shown for each sample.
during the purification process. These precursor molecules
can either be straight chain alkanethiols that lack the head Sample=
groups of the final product, or they can be molecules used to (soln percentage) C 1s O 1s S 2p Au 4f
introduce the thiol functional group to a precursor molecule
PEG4thiol (100%) 64.5 19.1 1.3 15.1
(such as thioacetic acid). Since these compounds also contain
thiol functionalities, they can compete with the alkanethiol PEG4thiol (100%) 65.3 20.9 1.2 12.6
of interest for available surface locations. Competitive
adsorption can be particularly problematic for alkanethiols PEG4thiol/TAA (99%/1%) 55.9 17.3 2.3 24.5
with complex or bulky head groups. Bulky head groups can PEG4thiol/TAA (99%/1%) 56.2 17.3 2.8 23.7
reduce the driving force for assembly by disrupting the close
packed arrangement of the alkane chains. With this reduced PEG4thiol/TAA (90%/10%) 45.6 12 4.3 38.1
driving force for assembly, the straight chain or small thiol
contaminants can out-compete the alkanethiol of interest on PEG4thiol/TAA (90%/10%) 46.2 13.6 4 36.2
the surface. =
PEG4 thiol = (1-mercapto-11-undecyl)tetra(ethylene glycol); Aldrich
Prod. No. 674508 TAA = thioacetic acid
These effects were noticed in early alkanethiol self-assembly
research and several detailed studies were performed on the Table 2 shows the data from Table 1 rescaled without the
preferential adsorption of one alkanethiol versus another. gold signal. This allows comparison of the atomic percentages
Adsorption from a dilute solution in ethanol of a mixture of with that expected based on the solution mixture atomic
two alkanethiols, one with a polar the other with a nonpolar composition. As seen in Table 2, the experimental values
head group, showed that adsorption of the alkanethiol with compare well with the calculated values. The atomic
the nonpolar head group was favored.7 Bain et al. also noticed percentage of sulfur is typically observed to be lower than
that alkanethiols with equivalent head groups, but longer expected due to attenuation by the overlying monolayer. This
chains adsorbed preferentially over shorter alkanethiols. 4 is the case for the 100% PEG4thiol. The fact that the sulfur
When one tries to intentionally obtain a mixed monolayer,
s i g m a - a l d r i c h . c o m
It is interesting to note that when looking at Table 2, one Self-Assembly: Unlimited Opportunities
might think that since the relative percentages of carbon and
SAMs have been used for studies and applications in many
oxygen do not change significantly from sample to sample,
areas. A few examples include surface wetting, non-fouling
that the surfaces are still pure PEG4 thiol. It is only the high
property, electrochemistry, surface passivation, protein binding,
percentage of sulfur that sets the samples apart and indicates
DNA assembly, corrosion resistance, biological arrays, cell
that an impurity is likely present.
interactions, and molecular electronics. These and other topics
Overall, this data demonstrates that even small amounts of have been summarized in previous review articles.11-13
contaminants in a solution can cause significant differences
SAMs have truly opened the doors toward direct surface
in the monolayer composition and structure. The best way
engineering. Only the imagination limits the possibilities
to avoid these problems is to use molecules with the highest
available to the interested researcher. Figure 2 shows
possible purities.
schematic diagrams of several possible applications for
Table 2. ESCA composition data from PEG4 thiol monolayers with and
alkanethiol monolayers. These types of applications will likely
without “impurities” rescaled without gold signal. All data is shown in rely on high purity alkanethiols with head groups such as
of Pure Alkanethiols
Monolayers: Advantages
Self-Assembled
atomic percent. Two analysis spots are shown for each sample. The values those listed in Table 3.
in bold are the calculated atomic percentages based on the solution mixture
ratio of the compounds used.
Sample= C 1s O 1s S 2p
PEG4thiol (100%) 76.0 22.5 1.5
PEG4thiol/TAA (90%/10%) 72.4 21.3 6.3 Figure 2. Possible applications for alkanethiol monolayers.
A) Non-fouling surfaces B) SAMs with specific binding receptors C) Cell
PEG4thiol/TAA (90%/10%-predicted) 73.4 20.5 6.1 supports for native cell growth and studies D) Molecular electronics
E) Microarrays F) Separations.
TAA (100%-predicted) 50 25 25
O r d e r :
=
PEG4 thiol = (1-mercapto-11-undecyl)tetra(ethylene glycol); Aldrich Table 3: Some head group examples useful for the applications
Prod. No. 674508 TAA = thioacetic acid shown in Figure 2.
1 . 8 0 0 . 3 2 5 . 3 0 1 0
present in PEG3 and PEG6 thiol samples. Both of these samples
showed a higher than expected gold and sulfur signals Specific binding receptors Biotin, NTA, Peptide,
indicating the layers were disordered and a sulfur contaminant Carbohydrates
was present. The most important property of poly(ethylene Cell supports Peptide
glycol) alkanethiols (PEGn thiols) is the ability to form a non- Molecular electronics CH3, SH
fouling self-assembled monolayer, but the presence of just Microarrays DNA, Peptide, PEGn
small amounts of carboxylic acid-terminated PEGn thiols
Separations NTA
(possibly introduced from poly(ethylene glycol) starting
material) leads to significant protein adsorption, making Surface reactions Azide, COOH, NH2, OH, SH
Te c h n i c a l
thiolated DNA onto the gold surface. The authors showed that Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc. 1987, 109,
3559. (7) Bain, C. D.; Evall, J.; Whitesides, G. M. J. Am. Chem. Soc. 1989,
when contaminated thiolated DNA was used for the assembly, 7155. (8) Nelson, K. E.; Gamble, L.; Jung, L. S.; Boeckl, M. S.; Naeemi, E.;
the atomic percentages of characteristic DNA elements (P, N) Golledge, S. L.; Sasaki, T.; Castner, D. G.; Campbell, C. T.; Stayton, P. S.
did not increase with increasing assembly times as they did Langmuir 2001, 17, 2807. (9) Roberts, B. J.; Naeemi, E.; Ratner, B. D. JURBIE
with purer samples. Increased assembly times instead resulted 2004, 4, 103-107. (10) Lee, C.-Y.; Canavan, H. E.; Gamble, L. J.; Castner,
1 . 8 0 0 . 2 3 1 . 8 3 2 7
D. G. Langmuir 2005, 21, 5134. (11) Love, J. C.; Estroff, L. A.; Kriebel, J. K.;
in increased amounts of the contaminant molecules on the
Nuzzo, R. G.; Whitesides, G. M. Chem. Rev. 2005, 105, 1103. (12) Chaki, N.
surface. Samples prepared from relatively pure DNA showed K.; Vijayamohanan, K. Biosensors & Bioelectronics 2002, 17, 1. (13) Ulman,
logical trends for the DNA elements in a time series assembly. A. Chem. Rev. 1996, 96, 1533.
For package sizes and prices of products in this matrix, please visit sigma-aldrich.com.
n\Head Group (-R) -H -OH -COOH -SH (Dithiols)
3 P50757 (99%) 405736 (95%) M5801 (99+%)
4 451878 (95%)
5 P7908 (98%)
6 234192 (95%) 451088 (97%) 674974 (90%) H12005 (96%)
7 H4506 (95%)
Self-Assembled
of Pure Alkanethiols
Monolayers: Advantages
OCH3
1H,1H,2H,2H-Perfluoro-1-hexanethiol CF3(CF2)2CF2
SH 98 16494-250MG 130.00
of Pure Alkanethiols
Monolayers: Advantages
Self-Assembled
11-Amino-1-undecanethiol, hydrochloride HS
NH2 HCl 99 674397-50MG 264.00
(1-Mercaptoundec-11-yl)tetra(ethylene O O
95 674508-250MG 129.00
glycol)l HS O O OH
(1-(Methylcarbonylthio)undec-11- O
O O
95 674176-250MG 91.90
H3C S O O OH
yl)tetra(ethylene glycol)
(1-Mercaptoundec-11-yl)hexa(ethylene HS O
O
O
O
O
O
OH 96.5 675105-250MG 270.80
glycol)
Hexa(ethyleneglycol)mono-11- O
O O O
95 675849-250MG 75.10
H3C
(acetylthio)undecylether S
O r d e r :
O O O OH
1 . 8 0 0 . 3 2 5 . 3 0 1 0
O ur NanoThinksTM solutions will help you get results faster by reducing prep time and
mixing errors. We feature our best selling thiol materials in a high-purity ethanol. Just
Te c h n i c a l
select the head group of the thiol and prepare your film. NanoThinksTM are ideal for use in
molecular assembly or dip-pen nanolithography applications. (The NanoThinksTM products are shown
on page 6 in the Alkane Thiols – Linear Chain Table.)
Visit our Web site at sigma-aldrich.com/selfassembly for more information and for our
S e r v i c e :
Ångstroms
intermolecular interactions in 1-AD SAMs. This process is called
microdisplacement. The process can be applied to intelligent
self- and directed- assembly7, 8 to fabricate nanoscale-
separated SAMs and improve chemical patterning techniques.
250 Å
0.0
Experimental
All SAMs were fabricated using 1-adamantanethiol (1-AD, 2.2
B
Aldrich Prod. No. 659452), 1-dodecanethiol (C12, Aldrich
Prod. No. 471364), and 1-octanethiol (C8, Aldrich Prod.
Ångstroms
No. 471836) on commercially available Au{111} that was
evaporated onto freshly cleaved mica substrates and annealed
using a hydrogen flame just prior to deposition. A single
component 1-AD SAM was created by immersing a gold
substrate into a 10 mM ethanolic 1-AD solution for 24 h. 50 Å
0.0
Subsequently, the gold substrate with the single-component
1-AD SAM was rinsed in neat ethanol and blown dry with Figure 1. Scanning tunneling microscopy image of a 24 h
nitrogen twice. 1-adamantanethiolate (1-AD) SAM on a Au{111} substrate. Image
parameters: Vsample = -0.75 V, Itunnel = 3.0 pA. A)
To fabricate separated C12 and 1-AD SAMs, a single- Resolution: 750 Å × 750 Å; shows several monatomic step edges and
component 1-AD SAM was immersed in a 1 mM ethanolic substrate vacancy islands. B) Resolution: 200 Å × 200 Å; molecular
C12 solution for a displacement time of 20 min and then resolution shows the 1-AD lattice.
rinsed in neat ethanol and blown dry with nitrogen twice. Both of these features are commonly observed in thiol
Representative scanning tunneling microscopy (STM) images SAMs. Additionally, 1-AD SAMs show depressed domain
were acquired for both the single-component 1-AD SAMs boundaries resulting from rotational domains of the 1-AD
and the separated C12 and 1-AD SAMs within 24 h of SAM molecules. This is in contrast to alkanethiolate SAM systems,
fabrication. From the STM images, the lattice structure, the which exhibit protruding domain boundaries associated
domain boundaries, and the molecular order of the SAMs with regions of molecules with differing tilts, rotational and
were investigated. All STM measurements were performed translational boundaries, and stacking faults.11-13 Figure 1 (B)
under ambient conditions using a custom beetle-style STM.9 shows a representative STM image with molecular resolution
Images were recorded in constant-current mode and at high of a single-component 1-AD SAM, showing individual
tunneling gap impedances (~1012 GΩ) to ensure large tip- molecules arranged in a hexagonally closed-packed structure
s i g m a - a l d r i c h . c o m
sample separation for minimal contact between the probe tip with nearest-neighbor spacing of 6.9 ± 0.4 Å. This lattice
and the monolayer. spacing is considerably larger than the nearest-neighbor
Microdisplacement-printed SAMs were fabricated by spacing for alkanethiolate SAMs and can be attributed to
contact of a C8 coated patterned elastomeric stamp with a the bulky carbon cage of 1-AD molecules compared to the
preformed single-component 1-AD SAM.7, 8 An elastomeric relatively compact (predominantly all-trans) alkyl chains of
alkanethiolates. A (7×7) unit cell can be assigned to the 1-AD the substrate only in places where the stamp and substrate
SAM with respect to the Au{111} substrate.5 Typical alkanethiol are in contact. However, this process is limited to molecules
SAMs exhibit a (√3×√3)R30° unit cell. This implies that there that are not susceptible to lateral diffusion across the
are 1.8 times more molecules in an alkanethiol SAM than in surface. Microdisplacement printing (µDp), is an alternative
a 1-AD SAM in the same area of Au{111}. For example, in a patterning technique not limited by lateral diffusion. In µDp,
(7√3×7√3)R30° unit area of Au{111}, which is the unit area a preformed 1-AD monolayer is used that is sufficiently labile
where the 1-AD and alkanethiolate unit cells overlap, there are to be displaced by patterned molecules through competitive
49 alkanethiolate molecules (21.4 Å2/molecule) and 27 1-AD adsorption while preventing lateral diffusion of the patterned
molecules (38.9 Å2/molecule). molecules.7,8 Figure 3 displays a LFM image of a patterned
Nanoscale-separated SAMs offer excellent opportunities to Au{111} substrate fabricated by µDp.
investigate the influence of intermolecular interactions on
the assembly of thin films, which is essential for the further
development of chemical patterning techniques.14, 15 Figure 2
(A and B) show representative STM images of separated C12
Printing
Microdisplacement
and 1-AD SAMs formed via C12 solution displacement of
preformed 1-AD SAMs.
7.1
A
Ångstroms
250 Å
0.0
10 µm
5.7
B
Figure 3: Lateral force microscopy (LFM) image of a patterned Au{111}
substrate made by microdisplacement printing. The low-friction (shown
Ångstroms
as dark) squares are the stamped octanethiol molecules, and the high-
friction (shown as light) background is the preformed 1‑adamantanethiolate
SAM. Image parameters: 40 µm × 40 µm, Scan rate = 1.0 Hz, Force
setpoint = 4 nN.
O r d e r :
50 Å
0.0 molecules, and the high-friction (shown as light) background
is the preformed 1-AD SAM. This pattern could not be formed
Figure 2. Scanning tunneling microscopy image of a separated using traditional µCp printing. µDp also eliminates the need
1-dodecanethiolate (C12) and 1-adamantanethiolate (1-AD) SAM on a
for solvent exposure after stamping. Solvent exposure is
1 . 8 0 0 . 3 2 5 . 3 0 1 0
Au{111} substrate. Image parameters: Vsample = -1.20 V, Itunnel = 1.0 pA.
A) Resolution: 1000 Å × 1000 Å; shows distinct domains of both lattice often required in µCp to prevent degradation of the pattern
types: C12 - more protruding molecular domains; 1-AD - less protruding over time, but the precision of the pattern is reduced due to
molecular domains; the most depressed regions are substrate vacancy molecular exchange. With microdisplacement printing, the
islands. B) Resolution: 300 Å × 300 Å; shows the molecular order of each 1-AD SAM is still present in places where the elastomeric
lattice type.
stamp did not contact the surface; thus, a solvent exposure
The apparent heights and the differences in lattice spacing step is not necessarily required. Multiple stamping steps can
were employed to differentiate between the C12 and also be used to create proximate structures, circumventing the
1-AD lattice types. The most protruding lattice with smaller difficulty in the precise registration of neighboring patterns in
molecular spacing that originates at the substrate defects conventional printing.8
Te c h n i c a l
displacement times result in larger C12 domains). At long patterning techniques by hindering the lateral movement of
C12 displacement times, the resulting SAM was completely molecules across a patterned surface.
composed of C12 molecules, although the C12 domains were
significantly smaller when compared to a single-component Acknowledgments
C12 SAM. The Air Force Office of Scientific Research, Army Research
1 . 8 0 0 . 2 3 1 . 8 3 2 7
Microcontact printing (µCp) is a technique for chemically Office, Defense Advanced Research Projects Agency, National
patterning a substrate by contact with an elastomeric Science Foundation, Office of Naval Research, Semiconductor
stamp that is inked with the molecules to be patterned.16 Research Corporation, and Sigma Aldrich are gratefully
Molecules on the stamp are transferred from the stamp to acknowledged for their support.
References
(1) Jeon, N. L.; Clem, P. G.; Nuzzo, R. G.; Payne, D. A., J. Mater. Res. 23, 2929. (9) Bumm, L. A.; Arnold, J. J.; Charles, L. F.; Dunbar, T. D.; Allara,
1995, 10, 2996. (2) Chen, C. S.; Mrksich, M.; Huang, S.; Whitesides, D. L.; Weiss, P. S., J. Am. Chem. Soc. 1999, 121, 8017. (10) Graham, D.
G. M.; Ingber, D. E., Biotechnol. Prog. 1998, 14, 356. (3) Handbook of J.; Price, D. D.; Ratner, B. D., Langmuir 2002, 18, 1518. (11) Delamarche,
Microlithography, Micromachining, and Microfabrication. SPIE: London, E.; Michel, B.; Gerber, C.; Anselmetti, D.; Guntherodt, H. J.; Wolf, H.;
1997. (4) Xia, Y. N.; Rogers, J. A.; Paul, K. E.; Whitesides, G. M., Chem. Ringsdorf, H., Langmuir 1994, 10, 2869.
Rev. 1999, 99, 1823. (5) Dameron, A. A.; Charles, L. F.; Weiss, P. S., J. Am. (12) Sellers, H.; Ulman, A.; Shnidman, Y.; Eilers, J. E., J. Am. Chem. Soc.
Chem. Soc. 2005, 127, 8697. (6) Dameron, A. A. Controlling Molecular 1993, 115, 9389. (13) Ulman, A.; Eilers, J. E.; Tillman, N., Langmuir 1989,
Assemblies. The Pennsylvania State University, University Park, 2006. (7) 5, 1147. (14) Lewis, P. A.; Donhauser, Z. J.; Mantooth, B. A.; Smith, R. K.;
Dameron, A. A.; Hampton, J. R.; Smith, R. K.; Mullen, T. J.; Gillmor, S. D.; Bumm, L. A.; Kelly, K. F.; Weiss, P. S., Nanotechnology 2001, 12, 231.
Weiss, P. S., Nano Lett. 2005, 5, 1834. (8) Dameron, A. A.; Hampton, J. (15) Smith, R. K.; Lewis, P. A.; Weiss, P. S., Prog. Surf. Sci. 2004, 75, 1.
R.; Gillmor, S. D.; Hohman, J. N.; Weiss, P. S., J. Vac. Sci. Technol., B 2005, (16) Wilbur, J. L.; Kumar, A.; Kim, E.; Whitesides, G. M., Adv. Mater. 1994,
6, 600.
Thiol Products
Product Description Structure Purity,% Product No.
Microdisplacement
Printing
Biphenyl-4,4′-dithiol HS SH
95 673099-1G 95.00
Alkane Disulfides
Alkane Disulfide Structure Purity,% Product No.
Undecyl disulfide S 99 674303-250MG 180.00
Hydroxyundecyl disulfide OH
99 674257-250MG 220.00
S
OH
O S
Hydroxyhexadecyl disulfide OH
S
99 674478-100MG 220.00
OH
S
OH S
S
O
Electronics
Self-Assembly in Flexible
active materials are future generations of products that which holes are injected and transported through the organic
may eventually enter mainstream electronics market. The material. It has been found that electrode surface modification
advantages in using organic active materials are their ease in with a self-assembled monolayer can be used to improve the
tuning electronic and processing properties by chemical design charge injection into the organic semiconductor.3 For example,
and synthesis, low cost processing based on low temperature when Au electrodes are used, they can be functionalized with
processes and reel-to-reel printing methods, mechanical various thiol SAMs to tune their work functions. Moreover, the
flexibility, and compatibility with flexible substrates.1 morphology of organic semiconductors is significantly different
Organic thin film transistors (OTFTs) are the basic building when deposited on SAM modified Au compared to bare Au.
blocks for flexible integrated circuits and displays. A schematic This observation has been used to tune the morphology of the
structure is shown in Figure 1.2 organic semiconductor at the Au/organic interface to improve
its charge injection.4
O r d e r :
on SiO2 surface (a typical dielectric material) is known to trap
electrons. Capping SiO2 surfaces with octadecyl trichlorosilane
(OTS) molecules can significantly reduce electron traps and
improve mobility of n-channel semiconductors (electrons are
the major charge carriers).5
1 . 8 0 0 . 3 2 5 . 3 0 1 0
Additionally, dielectric surface treatment with SAMs also
affects the nucleation and growth of organic semiconductors.6
For example, pentacene is an organic semiconductor with the
highest reported thin film charge carrier mobility. Its charge
Figure 1. Schematic structure of an organic thin film transistor. carrier mobility changes significantly depending on the types
(a) Chemical structure of the silane molecule used as the self-assembled
monolayer dielectric layer (b) Chemical structure of pentacene used as
of hydrophobic SAM surface treatment. This difference is
the semiconductor layer (c ) schematic structure of the device. Reproduced related to the morphological difference of the first pentacene
with permission from the Nature Publishing Group. monolayer formed on different surfaces.6
Te c h n i c a l
important roles in improving device performance as well as transistors.2 Other SAMs, as well as self-assembled multilayers,
enabling low cost processing methods for the fabrication of have also been reported as high performance dielectric layers
these devices. In this article, a briefly survey is given on the Figure 2.7,8 SAM initiators have been used for initiating
applications of self-assembly in OTFTs. surface polymerization to form dielectric layers Figure 3.9
Figure 2. Schematic representation of the components of an OTFT showing the molecular structures of various organic semiconductors (left) and self-
assembled nanodielectries I-III (right). Nanodielectric layers were deposited from solutions of silane precursors.
Ph Ph
S S [Ru] X
[Ru]
Ph Ph
Au Au
Semiconductor
Deposit Semiconductor, Polymer Dielectric
Drain / Source Electrodes
Au
Au
Si / SiO2
Figure 3. Modification of a gold gate electode for the surface initiated polymerization reaction to grow a dielectric layer.
Electronics
Self-Assembly in Flexible
Ho, P. K. H.; Sirringhaus, H.; Friend, R. H. Nature 2005, 434, 194. (6) Yang,
H. C.; Shin, T. J.; Ling, M. M.; Cho, K.; Ryu, C. Y.; Bao, Z. N. J. Am. Chem.
Soc. 2005, 127, 11542. (7) Collet, J.; Tharaud, O.; Chapoton, A.; Vuillaume,
D. Appl. Phys. Lett. 2000, 76, 1941. (8) Yoon, M. H.; Facchetti, A.; Marks,
T. J. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 4678. (9) Rutenberg, I. M.;
Scherman, O. A.; Grubbs, R. H.; Jiang, W. R.; Garfunkel, E.; Bao, Z. J. Am.
Chem. Soc. 2004, 126, 4062. (10) Tulevski, G. S.; Miao, Q.; Fukuto, M.;
Figure 4. Regioregular poly(3-hexylthiophene) spontaneously assemble into Abram, R.; Ocko, B.; Pindak, R.; Steigerwald, M. L.; Kagan, C. R.; Nuckolls,
ordered structures upon solution deposition. The pi-pi stacking between C. J. Am. Chem. Soc. 2004, 126, 15048. (11) Locklin, J.; Shinbo, K.; Onishi,
polymer chains facilitates change transport. K.; Kaneko, F.; Bao, Z. N.; Advincula, R. C. Chem. Mat. 2003, 15, 1404.
(12) McCullough, R. D. Adv. Mater. 1998, 10, 93. (13) Bao, Z.; Dodabalapur,
A.; Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108. (14) Sirringhaus, H.;
a b Tessler, N.; Friend, R. H. Science 1998, 280, 1741. (15) Sirringhaus, H.;
Kawase, T.; Friend, R. H.; Shimoda, T.; Inbasekaran, M.; Wu, W.; Woo, E. P.
Science 2000, 290, 2123. (16) Bao, Z. N.; Feng, Y.; Dodabalapur, A.; Raju,
V. R.; Lovinger, A. J. Chem. Mat. 1997, 9, 1299. (17) Zielke, D.; Hubler, A.
C.; Hahn, U.; Brandt, N.; Bartzsch, M.; Fugmann, U.; Fischer, T.; Veres, J.;
Ogier, S. Appl. Phys. Lett. 2005, 87. (18) Kagan, C. R.; Breen, T. L.; Kosbar,
L. L. Appl. Phys. Lett. 2001, 79, 3536. (19) Briseno, A. L.; Aizenberg, J.;
Han, Y. J.; Penkala, R. A.; Moon, H.; Lovinger, A. J.; Kloc, C.; Bao, Z. A. J.
Am. Chem. Soc. 2005, 127, 12164. (20) Xia, Y. N.; Rogers, J. A.; Paul, K. E.;
c d e Whitesides, G. M. Chem. Rev. 1999, 99, 1823. (21) Bao, Z.; Rogers, J. A.;
Katz, H. E. J. Mater. Chem. 1999, 9, 1895. (22) Zschieschang, U.; Klauk, H.;
Halik, M.; Schmid, G.; Dehm, C. Adv. Mater. 2003, 14, 1147.
O r d e r :
Figure 5. Optical micrographics of patterned arrays of organic
semiconductor crystals nucleated selectively on to self-assembled terphenyl
1 . 8 0 0 . 3 2 5 . 3 0 1 0
thiol template patterens: (a) and (b) anthracence crystals, scale bar = 200
mm; (c) large oriented sigle crystal of anthracene, scale bar = 50 mm (d)
patterned anthrancene crystalline films, scale bar = 300 mm; (e) patterned
single crystal of 5-chlorotetracence, scale bar = 100 mm
For package sizes and prices of products in this matrix, please visit sigma-aldrich.com
n\-R -OCH3 -OCH2CH3 -Cl
3 175617 (95%)
5 533386 (99%)
6 446963 (97%)
S e r v i c e :
(3-Glycidyloxypropyl)trimethoxysilane H3C
O
98 440167-100ML 26.80
Si
O
O 440167-500ML 88.70
O CH3 O
H3C
1H,1H,2H,2H-Perfluorooctyltriethoxysilane F2
C
F2
C
F2
C
OCH2CH3 97 667420-25G 220.00
F3C C
F2
C
F2
Si OCH2CH3 667420-5G 68.10
OCH2CH3
Cl
1H,1H,2H,2H-Perfluorodecyltriethoxysilane CF3(CF2)7CH2CH2Si(OCH2CH3)3
97 658758-25G 178.50
658758-5G 45.30
Methoxy(dimethyl)octadecylsilane CH3 >90 40955-100ML 325.00
CH3OSiCH2(CH2)16CH3
40955-25ML 119.00
CH3
Functionalized Polyelectrolytes
Polyelectrolytes are defined as materials for which properties in solvents with high dielectric constant are governed by
electrostatic interactions over distances larger than typical molecular dimensions.1,2 These materials have been successfully
applied in electrostatic self-assembly techniques3 for thin film deposition of electrically conducting polymers,4 conjugated
polymers for light emitting devices,5 nanoparticles,6 and nonlinear optical (NLO) materials.
Sigma-Aldrich offers a comprehensive selection of polyelectrolytes, anionic and cationic. Visit sigma-aldrich.com/selfassembly.
(1) Specialty Polymers; Dyson, R.W., Ed.; Chapman and Hall, 1987; p 110; Aldrich Prod. No. Z22,414-6. (2) For a discussion of the differences between
polyelectrolytes and ionomers, see: Eisenberg, A.; Kim, J-S. Introduction to Ionomers; John Wiley, 1998; Aldrich Prod. No. Z41,033-0. (3) Handbook of
Polyelectrolytes and Their Applications, 3 Volumes, Tripathy, S. et al., Eds.; American Scientific Publishers, 2002; Aldrich Prod No. Z54,718-2. (4) Sayre, C.N.;
Collard, D.M. J. Mater. Chem. 1997, 7, 909. (5) Cheung, J. et al. Polym. Prepr. 1993, 34, 757. (6) Schmitt, J. et al. Adv. Mater. 1997, 9, 61.
NanotethersTM
High Affinity Polyvalent
SensoPath
Technologies, Inc. hanging by only one hand from a tree branch, reaching for a
banana in a wind flow. Any monkey who lets go will be blown
Association of Sulfur with Gold away without the banana. If the monkeys were hanging by
both hands while reaching for a banana with their tails, then
Self-assembled monolayers or SAMs of thiols and organic
they would be exponentially more stable and much less likely
disulfides on gold surfaces were described by Nuzzo and
to be blown off the branch. Monkeys hanging by both hands
Allara in 19831 as a considerable improvement over difficult
and their tails would, of course, be ka3 more stable.
to maintain Langmuir-Blodgett monolayers. Extensive studies
by these authors and by the Whitesides group at Harvard
Monothiol vs Dithiol Monolayers
University led to a generally accepted conclusion that the
bonding state of an adsorbed thiol or disulfide on gold was Figure 1 shows that aromatic dithiol tethers (Aldrich Prod.
an Au-thiolate (Au0-S-) with a binding energy somewhere No. 674338) do in fact adsorb more quickly and provide more
between the binding energy for electrostatic interaction and surface coverage than aromatic monothiols (Aldrich Prod.
a covalent bond, based on X-ray-photoelectron spectroscopy No. 673560). The data were recorded on a Reichert 7000
(XPS), Auger electron spectroscopy, temperature-programmed Surface Plasmon Resonance (SPR) instrument by flowing the
desorption and high-resolution electron energy loss nanotethersTM (1 mM in 100% ethanol) over a clean gold SPR
spectroscopy 2–5. There is also indication that the disulfide slide then washing with 100% ethanol at a preset time.
association is much faster and more stable than a simple
monothiol association with the gold surface, a point we 30
will return to later in this article, and that the S-S bond of a
disulfide may be cleaved during adsorption to the Au(111) 25
O r d e r :
surface5 to yield the thiolate. On the other hand, an in-depth
X-ray diffraction study by Fentner et al.6 suggests that the 20
monolayer spacing (2.2 A°) of alkane thiols on Au(111) is close
enough to imply the existence of a disulfide bond between 15
1 . 8 0 0 . 3 2 5 . 3 0 1 0
adjacent alkane thiols. It is then possible to hypothesize that
the sulfur atoms may intercalate between the gold atoms, 10
thus accounting for the deprotonation of the thiol to thiolate
or disulfide and concomitant presence of Au0, as well as 5
enhanced binding energy and enhanced stability of the sulfur-
gold association beyond a simple electrostatic interaction. 0
0 500 1000 1500 2000 2500
T i me (s)
More is Better
Polyvalent interactions are one of the basic concepts of HO
Te c h n i c a l
HO
biological molecular recognition. Multiple ligand binding,
represented by polyvalent antibodies or oligomeric binding
subunits is characteristic of many bacterial toxins, as well
O O
as several enzyme systems and the well known example in O
(CH2)6SH (CH2)6SH HS(H2C)6
molecular assembly, the tetrameric strepavidin interaction with
biotin. Multiple interactions provide a far stronger association Aldrich Prod. No. 674338 Aldrich Prod. No. 673560
S e r v i c e :
than the affinity (KA) of single ligand for its target substrate.
This point has been extensively explored7 and in fact, discussed Figure 1. Monolayer formation by dithiol aromatic NanotetherTM (red) vs
in terms of stability of alkane thiol monolayers, which monothiol aromatic NanotetherTM (blue) followed by solvent wash. Arrow
indicates introduction of 100% ethanol wash.
spontaneously desorbed in solvent under ambient conditions
from gold, silver, platinum, or copper. Both desorption and The dithiol adsorption is significantly faster and after
1 . 8 0 0 . 2 3 1 . 8 3 2 7
self-exchange were observed although residual thiols that washing, the resulting dithiol monolayer has a higher
could not be desorbed were observed8. The resulting patchy refractive index (higher pixel number) than the monothiol
surface, however, left significant areas of metal exposed. The dendron monolayer suggesting better coverage. We believe
desorption-resorption phenomenon has been proposed as a the sharp drop upon initiation of ethanol wash is due to
while dithiol aromatic PEG mixed monolayers appeared to tethers (Nanotether™ BPA-HH, Aldrich Prod. No. 674370)
be homogeneous. XPS data for the same slides indicated in Figure 4 couple easily with any aldehyde, including
significantly more sulfur-gold interaction for the dithiol over aldehydes generated from glycosylated antibodies by sodium
the monothiol mixed self-assembled monolayers. periodate11,12 resulting in specific orientation of the antibody
The apparent stability of the dithiol mixed self-assembled without impairing antibody activity, rather than the random
monolayer may account for the observation that the detection orientation that results from EDC/NHS coupling to carboxyl-
ratio of Staphylococcus aureus binding compared to E. coli terminated tethers.
binding for a dithiol surface ratio was 2.3, while for the
monothiol surface was 1.29, indicating greater selectivity O O(CH2)5COOH
for the pathogen on the dithiol surface. In the same study,
flexible spacer with
nonspecific binding response was 133.3 for the monothiol
functionalized terminus
surface and 39 for the dithiol surface10.
(CH2)6SH (CH2)6SH
hydrophobic module
Future Outlook
Monodisperse macromolecules including flexible linear, rigid-
rod and dendritic segments offer unique design capabilities
that allow positioning of a variety of ligands through
multivalent attachment functionalities while controlling the
Monothiol Mixed Self-assembled Monolayer ultimate flexibility of the tether. These types of constructs can
be functionalized for attachment to various surfaces and, on
their other terminus, functionalized for covalent coupling of
proteins, peptides, and small organic ligands, all of which can
be varied independent of one another and be connected to
each other through spacers with varying degrees of rigidity. A
hydroxyl terminus, for example Nanotether BPA (Aldrich Prod.
No. 674346) either alone or as part of a poly(ethylene glycol)
module, provides an excellent antifouling surface.
The rigid-rod (bisphenolA) modular construct shown in
Figure 3 contains a flexible alkane spacer with functional
terminus for attachment of ligand. In effect, it becomes a
“nano fishing rod” for many different assay applications in
which the ligand may be presented as if it were on a cell
membrane. A typical application is shown in Figure 4 in which
antibody capture ligand (the “bait”) has been covalently
s i g m a - a l d r i c h . c o m
glycosylated antibody the coupled (or “bait”) ligand from swinging back onto the
+
AFM tip where it may become ensnared. Considering other
O O(CH2)5CONHNH2
modular approaches, it is possible to modify the thiol terminus
O O
by substituting orthopyridinium disulfide or other coupling
bait reagents, linking the NanotetherTM to carbon nanotubes
S S
through the carboxyl terminus, or through a triethoxysilane
terminus to provide a 3-point attachment for coupling
to glass. Applications are limited only by a researcher’s
imagination.
O(CH2)5CONHN:C References
Biosensor Program
Biotechnology
rod O
(1) Nuzzo, R.G.; Allara, D.L., J. Am. Chem. Soc. 1983, 105, 4481. (2) Bain,
line
O
C.D.; Biebuyck, H.A.; Whitesides, G.M., Langmuir 1989, 5, 723. (3) Bain,
O
C.D.; Troughton, E.B.; Tao, Y.-T.; Evall, J.; Whitesides, G.M.; Nuzzo, R.G.,
flexible arm J. Am. Chem. Soc. 1989, 111, 321. (4) Biebuyck, H.A.; Whiresides, G.M.,
S
Langmuir 1993, 9, 1766. (5) Nuzzo, R.G.; Zegarski, B.R.; Dubois, L.H., J.
S
Am. Chem. Soc. 1987, 109, 733. (6) Fenter, P.; Eberhardt, A.; Eisenberger, P.,
Science 1994, 266, 1216. (7) Mammen, M.; Choi, S.-K.; Whitesides, G.M.,
Figure 4. Tethering an oxidized antibody to a hydrazide-terminated tether
Agnew. Chem. Int. Ed. Engl. 1998, 37, 2754. (8) Schlenoff, J.B.; Li, M.; Ly,
H., J. Am. Chem. Soc. 1995, 117, 12528. (9) Ramachandran, G.K.; Hopson,
T.J.; Rawlett, A.M.; Nagahara, L.A.; Primak, A.; Lindsay, S.M., Science 2003,
300, 1413. (10) Subramanian, A.; Irudayaraj, J.; Ryan, T., Sensors and
Actuators B 2005, online www.sciencedirest.com, 1. (11) Hermanson, G.T.,
Bioconjugate Techniques. Academic Press: San Diego, 1996; p 785. (12)
Spangler, B.D.; Tyler, B.J., Anal. Chim. Acta 1999, 399, 51.
Polyvalent Alkane Thiols – NanotethersTM
Product Description Structure Purity,% Product No.
Nanotether OH HO
96.5 674338-50MG 150.00
O O
(CH2)6SH (CH2)6SH
HS(H2C)6 O
O r d e r :
Nanotether BPA-HA HS(H2C)6 O
O O(CH2)6COOH
96.5 674354-50MG 350.00
HS(H2C)6 O
Nanotether BPA-HH O
96.5 674370-50MG 367.00
1 . 8 0 0 . 3 2 5 . 3 0 1 0
O O
O(CH2)6CONHNH2
(CH2)6SH (CH2)6SH
TM
Nanotethers is a trademark of Sigma-Aldrich Biotechnology, L.P.
films. A recommended protocol for preparing SAMs is outlined wash bottle used for rinsing containers, substrates and SAMs.
in this article. Store the bottle empty and only fill it with fresh ethanol when
needed.
Equipment and Materials
Equipment Checklist and Considerations Step-by-Step Procedure
This general protocol is appropriate for most thiols. Thiols
1. Gold coated substrates (See pg 10 for our substrates) containing amine, carboxy groups require modifications to
2. Thiol compound(s) the protocol as noted in green below. The properties of PEG
3. Fresh 200 proof ethanol (or appropriate solvent) thiol monolayers depend on the method of self-assembly.
4. Calibrated micropipettes Researchers should review references 5–7 before using these
5. Container for mixing thiol solution (solution container) materials.
6. Tweezers for sample handling
7. A dedicated ethanol solvent bottle 1. Determine necessary amounts and concentration of
8. Parafilm for sealing containers thiol solution.
9. Containers for sample preparation (sample containers) a. Calculate the total volume of thiol solution needed to make
10. Petri dishes for transporting and storing SAMs the number of samples desired.
11. Dry nitrogen [Total volume of solution (mL)] = [total number of samples] x
12. Analytical Balance [Sample solution volume (mL)]
13. Sonicator
b. C
alculate the total amount of thiol needed to prepare
14. pH paper
desired amount of solution. (where C = 1-5 mM solutions)
Environment: A clean environment is key to preparing quality
[Mass of thiol (g)] = [Total Volume (mL)] x [C x 10-6 mol/ml] x
SAMs. Low levels of contaminants can affect monolayer
[MW(g/mol)]
quality. Avoid rooms or hoods in which silanes or poly(dimethyl
siloxane) (PDMS) have been used. These compounds easily cross If the thiol is a liquid, you can convert the mass to a volume
contaminate a variety of surfaces. Iodine adsorbs readily onto using the density of the thiol. Use a calibrated micropipette for
gold and should be avoided. measuring and dispensing liquid thiols.
Handle all thiols in a fume hood. Most thiols have an obnoxious 2. Preparing the thiol solution. Prepare enough solution for
odor and are toxic (check MSDS before using). all samples to ensure the solution concentration is constant
across the sample set. When preparing mixed thiol solutions,
Containers: Appropriate containers include glass or
prepare a stock solution of each thiol separately, then mix
polypropylene (e.g., scintillation vials, polypropylene test
them at the proper proportions for the final stock solution.
tubes and centrifuge tubes). Glass containers must be cleaned
thoroughly to avoid solution contamination. a. R
inse all assembly containers with solvent by squirting ~3 to
5 mL around the inside of the containers. Repeat 2–3 times
Containers that can be easily sealed are recommended. For the
and re-cap each container. Rinse all beakers, tweezers,
highest quality films, oxygen exposure should be minimized
etc., to be used in the experiment with solvent. Label all
during the assembly process. This is achieved by reducing the
containers.
headspace above the thiol solution and backfilling with an
inert gas. Each substrate is placed in its own container to avoid b. M
easure the appropriate volume of solvent into the clean
interactions that would be detrimental to film quality. solution container.
1
One option for glass cleaning is the use of piranha solution (30:70 v/v c. Dispense the mass (or volume) of thiol, to the solvent.
solution of 30% hydrogen peroxide (H2O2) and concentrated sulfuric acid d. Sonicate the container 5–10 min to dissolve.
(H2SO4)). Extreme caution has to be taken when using piranha solution. e. Once dissolved, dispense the planned volume of solution
It is a very strong oxidant and reacts violently with organic matter.
s i g m a - a l d r i c h . c o m
•C
arboxy terminated thiols: Adjust the solution pH to ~2 200 Proof Ethanol
with a few drops of concentrated HCl. Then sonicate stock Sigma-Aldrich simplifies your purchase of 200-proof ethanol
solution. by immediately filing ATF paperwork and paying the federal
•A
mine terminated thiols: Adjust the solution pH to ~12 with excise tax for you!
concentrated NH4Cl or triethylamine. Then sonicate stock
solution. 459844-1 L ACS reagent, ≥99.5%
459836-1 L Anhydrous, ≥99.5%
3. Sample Self-Assembly.
459828-1 L HPLC/spectrophotometric grade
a. Immerse gold substrate in container containing the thiol
solution. Handle gold substrates with tweezers and E7023-500 mL Absolute for molecular biology
minimize expose to air, to reduce surface contaminants. 493546-500 mL USP/NF
b. B
ackfill each container with dry nitrogen and seal the cap For a complete list of our Tax-Paid Ethanol’s, please visit us at
sigma-aldrich.com/solvents and select High-Purity dropdown.
and wrap the cap with Parafilm.
c. S tore the sample for at least 24 to 48 hours. In general,
Labware for SAMs
Preparation
Protocol for SAMs
longer assembly times tend to result in better packing of the
monolayers. Find these Labware products
on our Web site at
4. T
erminating self-assembly: Functional groups on the sigma-aldrich.com/labware
thiols affect self-assembly termination.
keyword search:
For simple alkanethiols: microcapillary pipettes,
a. H
old the sample with clean tweezers and rinse with solvent tweezers, sigma-aldrich wash,
for 10 to 15 seconds from a clean solvent bottle. bottles (ethanol), parafilm,
scintillation vials or test
b. Dry sample with a stream of dry nitrogen.
tubes, petri dishes, analytical
For thiols with hydrogen-bonding, polar or bulky head groups: balances, sonicator, pH paper
c. H
old the sample with clean tweezers and rinse with solvent Ultrasonic Cleaner
for 10 to 15 seconds from a clean solvent bottle. (Solvent
should be pH adjusted for carboxy and amine terminated
SAMs)
d. P lace each sample in a container with fresh solvent and Coming Soon!
close the cap. (Again solvent should be pH adjusted if The NEW 2007–2008
needed)
Aldrich Handbook of Fine Chemicals
e. Sonicate the samples for 1–3 minutes.
Includes a Materials Science Application Index with
f. R
emove the samples individually and rinse again for 10–15 products organized in application
O r d e r :
seconds under a steady stream of ethanol. (At this stage no
groups for easy reference
pH adjustment is necessary. Use pure solvent)
and browsing.
g. Dry sample with a stream of dry nitrogen.
1 . 8 0 0 . 3 2 5 . 3 0 1 0
5. Sample Storage
a. Place in clean Petri dish.
b. Backfill Petri dish with dry nitrogen.
c. F or long-term storage: Place the Petri dishes in a jar
backfilled with dry N2 and sealed with Parafilm.
Topics
If you are going to use the monolayers for further • Chemical Solution Deposition/Sol-Gel Processing
experimentation, plan your experiments so you can rinse the • Chemical Vapor Deposition
samples right before use. Minimize time between preparation • Conducting Polymers
Te c h n i c a l
and use since SAMs can oxidize over time. • Fuel Cells
References
- Materials for Hydrogen Storage
(1) Love, C.; Estroff, L.; Kriebel, J.; Nuzzo, R.; Whitesides, G.; Chem. Rev., - Proton Exchange Membrane (PEM) Materials
2005, 105, 1103–1170. (2) Arnold, R.; Azzam, W.; Terfort, A.; Woll, C., • Nanoparticles
Langmuir, 2002, 18, 3980–3992. (3) Wang, H.; Chen, S. F.; Li, L. Y.; Jiang, - Nanopowders & Nanodispersions
S. Y., Langmuir, 2005, 21, 2633–2636. (4) Noh, J.; Konno, K.; Ito, E.; Hara, - Functionalized Nanoparticles
S e r v i c e :
M., Jpn. J. Appl. Phys. Part 1 2005, 44, 1052–1054. (5) Li, L. Y.; Chen, - Quantum Dots
S. F.; Zheng, J.; Ratner, B. D.; Jiang, S. Y., J. Phys. Chem. B 2005, 109, • Electronic Grade Materials
2934–2941. (6) Herrwerth, S.; Eck, W.; Reinhardt, S.; Grunze, M., J. Am.
Chem. Soc. 2003, 125, 9359–9366. (7) Harder, P.; Grunze, M.; Dahint, R.; Reserve Your Free Copy of the
Whitesides, G. M.; Laibinis, P. E., J. Phys. Chem. B 1998, 102, 426–436 Aldrich Handbook Today!
sigma-aldrich.com/handbook2
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